Preparation of phosphatides



Patented Feb. 15, 1949 2,461,751

UNlT-ED STATES-PATENT OFFICE Ralph A. Marmor and Wendell W. Moyer, Decatur, Ill., assignors to A. E. Staley Manufacturing Company, Decatur, Ill., a corporation of Delaware No Drawing. Application June 17, 1947, Serial No. 755,257

3 Claims. (Cl. 260-403) This invention relates to improvements in the usually contains 60 to 65 per cent phosphatides. preparation of phosphatides from oleaginous ma- At present, this is one of the principal commercial terials, particularly to such preparation wherein methods for manufacturing phosphatides. glyceride oil and phosphatidic material are jo y Although l g quantities of Crude p extracted from the oleaginous material with a vtides'are easily and economically manufactured liquid solvent, followed by bleaching or decolorizas described above, such material has not found ing at low temperature preferably prior to solvent the anticipated application in many potential removal. uses, particularly in foodstuffs, because of its A primary object of the invention-is to improve dark color and strong odor. Heretofore, it has the color and odor of phosphatides obtained been necessary to decolorize and at least partially jointly with glyceride oils by extracting oleagi- \to deodorize the crude phosphatidic material benous material therefrom with a solvent for the fore it could be satisfactorily used in foodstuifs. glyceride oils contained therein. Although several conventional methods are Another object of the invention is to reduce or available for improving the color and odor of this eliminate the decolorization of the recovered material, all possess one or more drawbacks with phosphatides heretofore required to make them respect to processing time, apparatus required,

acceptable for many uses, chiefly in foodstuffs. cost of reagents, and the like.

Additional objects of the invention will be ap- The objectionable color and odor of crude parent from the description and claims that phosphatides obtained by conventional extraction follow, methods are apparently due to the high tempera- The invention accordingly comprises the sev' tures employed to free the extracted oil of solvent. eral steps and the relation of one or more of The bulk of the solvent is evaporated from the such steps with respect to each of the others extract or'micella at atmospheric pressure and thereof, which will be exemplified in the process the remainder is distilled off under reduced preshereinafter disclosed, and the scope of the applisure, frequently with the aid of injected supercation of which will be indicated in the claims. heated steam. During the latter operation, the

It is well known that many oleaginous mateoil is commonly heated to temperatures as high rials, especially those of vegetable origin, conas 100 to 120 C. and held there for substantial tain appreciable proportions of phosphatides, periods of time. Prior to this, the oil is also held frequently referred to as lecithin. Among these .for considerable periods of time at and above the materials are soybeans, cottonseed, corn germs, boiling point of the solvent. In the case of rape seed,'peanuts, and linseed, Attempts have hexane, the solvent most widely used at present,

been made heretofore to recover phosphatides the temperature of prior heating referred to from oleaginous materials by extracting the ranges from about 70 to 100 C.

latter with solvents in which the phosphatides We have discovered that the color and odor are preferentially soluble. Such attempts have of crude phosphatides obtained by extracting not proven satisfactory because the extracted oleaginous material with a solvent for glyceride phosphatides were always contaminated with oil, oils and treating the extracted oil with water pigments, and other materials which had to be as described above can be greatly improved by separated from the former'at considerable ex- 40 combining low temperature evaporation of solpense. vent from the extract with decolorization either It is also known that the conventional solvent of the oil obtained therefrom. The pronounced extraction of glyceride oils from oleaginous mabeneficial effects of this combination of steps are terial extracts a large part of the phosphatides apparently due in part to preventing a fixing in the oleaginous material with the oil, and that or setting of the color bodies by the high tem-t such jointly extracted phosphatides can bereadily peratures conventionally used in evaporating coagulated by stirring the oil vigorously with small solvent from the micella, and in part to preproportions of water. The ratio of extracted oil venting the formation of odorous materials by to extracted phosphatides is large, usually exthe heating during solvent removal, the latter ceeding 20 to 1. The 'so-called gum or crude materials being independent of color bodies afphosphatidic material thus obtained is a hydrosol fected by bleaching agents and color adsorbents.

consisting chiefly of water,'oil and phosphatides. The order in which the solvent is removed and Minor constituents frequently present include the oil is decolorized does not materially affect fatty acids, proteinaceous materials, sterol dethe quality of the phosphatides. We prefer to decolorize solution of oil in solvent, either as a rivatives, and color bodies. When dried the gum I):

' 3 full or partial micella, first, mainly because such solutions are more fiuid than the undiluted oil and are therefore more easily percolated or filtered through a bed of the adsorbent material, However, the advantages of this invention also may be obtained by first evaporating the solvent from the micella at low temperature, and then decolorizing the residual oil at suitably low temperature, either in the absence or presence of a diluent;

Any of the color adsorbents and bleaching agents conventionally used for decolorizing glyceride oils are suitable for the practice of our invention. Among the color adsorbents which may be used are activated carbon, magnesia, alumina, and clay, and among the bleaching agents may be mentioned hydrogen peroxide, benzoyl peroxide, chlorine dioxide, and sulfur dioxide. The color adsorbents may be activated byanypf the methods well known in the art.

In accordance with this invention, crude phosphatidesof markedly superior color and odor can be subsequently obtained from solvent extracted glycerlde oils if, prior to refining operations in-' volving temperatures exceeding about 50 C. the oil is treated with a color adsorbent and the solvent is evaporated from the oil, both operations being performed at temperatures not exceeding about 50 C. It is the combination of low temperature solvent removal and coloradsorption' that is important. As mentioned earlier, the order in which the two steps of the combination are performed does not materially affect the quality of the phosphatides.

In the preferred practice of our invention, the

full micella is stirred with a color adsorbent at temperatures not exceeding about 50 C. until color adsorption reaches substantial equilibrium. This usually does not require more than about one hour. Alternatively, the micella may be passed through a bed or column of the adsorbent. The decolorized micella, filtered if necessary, is then distilled under reduced pressure. and at a maximum liquid temperature of about 50- C. until no more than about one or two per cent solvent remains in the oil. The vaporized solvent may be recovered by conveying it to an efficient surface residual solvent does not interfere with coagulation of the phosphatides with an aqueous me dium. The following examples illustrate our invention: a

' Example 1 Flaked soybeans were extracted in a conventional manner with so-called hexane to provide an extract or full micella comprising about one part soybean oil to three parts hexane. Six liters of this micella was agitated with about 30 grams of an acid activated bleaching clay for about one hour at 25 to 30 C. The clay was filtered from the mixture, and the noticeably decolorized micella was vacuum distilled at a maximum liquid temperature of about C. until the residual oil contained about 2 per cent hexane. The substantially solvent-free oil thus obtained was then stirred vigorously for several minutes at about 50 C. with about 2 per cent of water and allowed to stand until the hydrated phosphatides settled out. This required about four hours. Supernatant oil was decanted from settled phosphatides and the latter, together with adhering oil, were transferred to bottles and centrifuged to separate additional adhering oil from the phosphatides. The phosphatidic material thus obtained was much lighter colored and less odorous than conventional preparations. Example 2 Dried corn germs were substituted for the flaked soybeans in Example 1. The phosphatides thus obtained from the crude solvent extracted corn oil were much lighter colored and of a more pleasant odor than phosphatide obtained by water washing conventional crude solvent extracted corn oil.

Example 3 The activated carbon, alumina, and magnesia were selected from the types commonly used in the refining of glyceride oils.

Example 4 Flakedsoybeans were extracted in a conventional manner with hexane to provide an extract or full micella comprising about one part soybean oil to three parts hexane. Six liters of this micella was stirred for three hours at 50 C. with 10 grams of powdered benzoyl peroxide, then filtered to remove any unreacted peroxide. The

filtered and noticeably decolorized micella was vacuum distilled at a maximum liquid temperature until the residual oil contained about 2 per cent hexane. The substantially solvent-free oil thus obtained was then stirred vigorously for several minutes atabout 50 C. with about 2 per cent of water and allowed to stand until the hydrated phosphatides settled out. This required about four hours. Supernatant oil was then decanted from the settled phosphatides, and the latter, together with adhering oil, were trans-- ferred to bottles and centrifuged to separate additional adhering oil from the phosphatides. The phosphatidic material thus obtained was much lighter colored and 'less odorous than conventional preparations.

Substitution of dried corn germs for the flaked soybeans in the preceding example resulted in crude phosphatides of equally improved color and odor.

Example 5 Flaked soybeans were extracted in a conventional manner with hexane to provide an extract or full micella comprising about one part soybean ofl and three parts hexane. Six liters of this micella was vacuum distilled at a maximum liquid temperature of about 50 C. until the residual' oil contained about 2 per cent hexane. This oil was stirred with 30 grams of an acid activated clay forabout one hour at 25 to 30 C., filtered to remove the clay, then agitated vigorously with about 2 per cent of. water at 50 C. for several minutes, and allowed to stand quietly until the coagulated phosphatides settled out. This required about four hours. Supernatant oil was decanted from the settled phophatides and the latter, together with adhering oil, were transferred to bottles and centrifuged to separate additional oil from the phosphatides.

l v I The phosphatidic material thus obtained was also markedly superior in color and odor to those qualities of conven tional preparations.

If desired, the phosphatides may be coagulated with the aqueous medium at temperatures higher than those employed in the foregoing examples, providing the mixture of oil and coagulated phosphatides is not maintained at the higher temperatures for extended periods of time. For example, coagulation temperatures of 80 to 90 C.

ever, because the phosphatides obtained will be contaminated with the corresponding salts of any free fatty acid present in the crude oil. And if the aquous solution is a concentrated solution of caustic alkali, such as is commonly used in the alkali refining of glyceride oils, partial saponification of the phosphatides is apt to oc- Phosphatides manufactured in accordance vide an extract containing glyceride oils, phosphatides, and solvent, decolorizing the extract,

evaporating solvent from the decolorized extract at a temperature not exceeding about 50 C. to provide a mutual solution of the remaining glyceride oils and phosphatides, agitating said solution with an aqueous medium to coagulate the phosphatides, and separating the coagulated phosphatides from the bulk of the glyceride oils.

2. The process of recovering phosphatides from oleaginous material which comprises extracting the oleaginous material with a solvent selected from the group consisting of hexane, trichloroethylene, benzene and ethanol to provide an extract containing glyceride oils, phosphatides, and solvent, evaporating solvent, from the-extract at a temperature not exceeding about 50 C. to pro vide a mutual solution of remaining phosphatides with this invention have a number of known and potential uses. Among these are reducing the viscosity of chocolate materials, preventing the foaming and spattering of heated margarine,

facilitating the wetting of powders and textiles, and improving the quality of lubricating oil.

v Any of the solvents conventionally used for the extraction of glyceride oils from oleaginous material may be used in the practice of the invention. The currently preferred solvent is socalled hexane, a high test gasoline boiling overv the range of about 63 to 70 C. Other solvents such as trichloroethylene, benzene, and ethanol, all having boiling points under 100 C., have been used.

It is not essential to successful coagulation of phosphatides from solvent extracted glyceride oils with an aqueous medium that all the solvent be evaporated from the oil. The maximum proportion of solvent that may remain with the oil and 'still permit good coagulation of the phosphatides varies with the kind of solvent. In general, however, as much as 15 to 20 per cent of solvent may be tolerated in the oil from which phosphatides are to be prepared in accordance with this invention.

Since certain changes may be made in carrying out the above process without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. 7

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.

We claim:

1. The process of recovering phosphatides from oleaginous material which comprises extracting the oleaginous material with a solvent selected from the group consisting of hexane, trichloroethylene, benzene and ethanol to proand glyceride oils, decolorizing said solution at a temperature not exceeding about 50 C., then agitating the decolorized solution with an aqueous medium to coagulate the phosphatides, and

separating the coagulated phosphatides from the bulk of the glyceride oils.

3. The process of recovering phosphatides from oleaginous material which comprises extracting the oleaginous material with hexane to provide an extract containing glyceride oils, phosphatides, and hexane, decolorizing the extract, evaporatmg hexane from the decolorized extract at a temperature not exceeding about 50 C. to provide a mutual solution of the remaining glyceride .oils and phosphatides, agitating said solution with an aqueous medium to coagulate the phosphatides, and separating the coagulated phosphatides from the bulk of the glyceride oils.

4. The process of recovering phosphatides from oleaginous material which comprises extracting the oleaginous material with trichloroethylene to provide an extract containing glyceride oils, phosphatides, and trichloroethylene, decolorizing the extract, evaporating trichloroethylene from the decolorized extract at a temperature not exceeding about 50 C. to provide a mutual solution of the remaining glyceride oils and phosphatides, agitating said solution with an aqueous medium to coagulate the phosphatides, and separating the coa'gulated phosphatides from the bulk of the glyceride oils. I

5. The process of recovering phosphatides from oleaginous material which comprises extracting the oleaginous material with benzene to provide an extract containing glyceride oils, phos phatides, and benzene, decolorizing the extract, evaporating benzene from the decolorized extract at a temperature not exceeding about 50 C. to provide a'mutual solution-of the remaining glyceride oils and phosphatides, agitating said solution with an aqueous medium to coagulate the phosphatides, and separating the coagulated phosphatides from the bulk of the glyceride oils.

6. The process of recovering phosphatides from flaked soybean material which comprises extracting the material with a solvent selected from the group consisting of hexane, trichloroethylene, benzene and ethanol to provide an extract containing soybean oil, phosphatides, and solvent, decolorizing the extract, evaporating solvent from the decolorized. extract at a temperature not exceeding about 50 C. to provide a mutual solution of the remaining soybean oil and phosphatides, agitating said solutionwith an aqueous medium to coagulate the phosphatides, and separating the coagulated phosphatides from the bulk of the soybean oil.

linseed material which comprises extracting-the material with a solvent selected from the group consisting of hexane, trlchloroethylene, benzene and ethanol to provide an extract containing linseed oil, phosphatides, and solvent, decolorizing the extract, evaporating solvent from the decolorired extract at a temperature not exceeding about 50 C. to provide a mutual solution 01' the remaining linseed oil and phosphatides, agitating said solution with an aqueous medium to coagulate the phosphatides, and separating, the coagulated phosphatides from the bulk of the linseed oil.

8. The process or recovering phosphatides from corn germ material which comprises extracting the material with a solvent selected from the group consisting of hexane, trichloroethylene, benzene and ethanol to provide an extract containing corn germ oil, phosphatides, and solvent, decolorizing the extract; evaporatingsolvent from the decolorized extract at a temp rature not exceeding about 50 C. to provide a, mutual solution of the remaining corn germ oil and phos- V REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,667,767 Bollman May 1, 1928 2,288,441 Ewing June 30, 1942 2,340,104 Brown Jan. 25, 1944 

